Sulfur containing polymers are very important as rubbers, conducting materials, and high performance polymers. Examples are poly(aliphatic disulfide)s, poly(phenylene sulfide) (PPS), poly(sulfone), and polybenzothiazole. Several new polymerization reactions have been described in this thesis for the preparation of sulfur containing materials. / The synthesis of a series of cyclic(arylene disulfide) oligomers was accomplished by catalytic oxidation of arylenedithiols with oxygen in the presence of a copper-amine catalyst. The cyclic(arylene disulfide) oligomers underwent a novel free radical ring-opening polymerization at elevated temperatures in the melt to form high molecular weight poly(arylene disulfide)s. Cyclic(arylene disulfide) oligomers were copolymerized with elemental sulfur at 250°C to form stable poly(arylene sulfane)s containing 3--7 sulfur linkages. They also copolymerized with diiodoaromatic compounds, or dibromoaromatic compounds, in the presence of potassium iodide at 270°C to give poly(thioaryiene)s with the formation of iodine as the coproduct in both cases. / The novel self-polymerization of 4-bromobenzenethiol was realized at 270°C in m-terphenyl solution in the presence of a catalytic amount of free radical initiator. Hydrogen bromide is the sole side product. This novel reaction has also been extended to the synthesis of poly(thioarylene)s from arylenedithiols and dibromoaromatic compounds. / Another novel polymerization reaction to prepare poly(arylene thioether)s has been realized by a one-pot reaction of bis(N,N'-dimethyl-S-carbamate)s with activated dihalocompounds in diphenylsulfone in the presence of a mixture of Cs2CO3/CaCO3. Bis(N,N'-dimethyl-S-carbamate)s can be conveniently prepared from dihydroxy compounds via the Newman-Kwart rearrangement reaction. This polymerization reaction opens a new route for the synthesis of new poly(arylene thioether)s and poly(arylene sulfone)s. / A series of novel cyclic(arylene ether)s has also been synthesized and characterized. The ring-opening polymerization of these cyclic oligomers in the melt represents a new way to prepare high performance polymers.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.34719 |
| Date | January 1997 |
| Creators | Ding, Yong. |
| Contributors | Hay, Allan S. (advisor) |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 001616822, proquestno: NQ44410, Theses scanned by UMI/ProQuest. |
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